JP5655141B2 - Silicate luminescent material and preparation method thereof - Google Patents
Silicate luminescent material and preparation method thereof Download PDFInfo
- Publication number
- JP5655141B2 JP5655141B2 JP2013516956A JP2013516956A JP5655141B2 JP 5655141 B2 JP5655141 B2 JP 5655141B2 JP 2013516956 A JP2013516956 A JP 2013516956A JP 2013516956 A JP2013516956 A JP 2013516956A JP 5655141 B2 JP5655141 B2 JP 5655141B2
- Authority
- JP
- Japan
- Prior art keywords
- luminescent material
- silicate luminescent
- preparing
- range
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000000463 material Substances 0.000 title claims description 69
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 title claims description 51
- 238000002360 preparation method Methods 0.000 title claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 66
- 150000001875 compounds Chemical class 0.000 claims description 31
- 239000000377 silicon dioxide Substances 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- 239000004965 Silica aerogel Substances 0.000 claims description 16
- 230000005284 excitation Effects 0.000 claims description 15
- 238000010894 electron beam technology Methods 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 13
- 238000010304 firing Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 9
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 7
- 229910052746 lanthanum Inorganic materials 0.000 claims description 7
- 229910052727 yttrium Inorganic materials 0.000 claims description 7
- 229910002651 NO3 Inorganic materials 0.000 claims description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 229910052684 Cerium Inorganic materials 0.000 claims description 5
- 229910052765 Lutetium Inorganic materials 0.000 claims description 5
- 229910052771 Terbium Inorganic materials 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims 1
- 239000000843 powder Substances 0.000 description 12
- 238000000295 emission spectrum Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- 238000010532 solid phase synthesis reaction Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 6
- 230000001133 acceleration Effects 0.000 description 4
- 101710134784 Agnoprotein Proteins 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 150000003891 oxalate salts Chemical class 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 2
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 1
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000004964 aerogel Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
- C09K11/77742—Silicates
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Luminescent Compositions (AREA)
Description
本発明は発光材料技術分野に関し、具体的には珪酸塩発光材料及びその調製方法に関する。 The present invention relates to the technical field of luminescent materials, and more specifically to a silicate luminescent material and a method for preparing the same.
６０年代、電界放出陰極アレー（ＦＥＡｓ）に基づく電子ビームマイクロ型装置の発想がＫｅｎ Ｓｈｏｕｌｄｅｒによって提出されたため、ＦＥＡｓを使用してパネルディスプレイ及び光源素子を設計及び製造する研究は一般に極めて大きな興味を引き起こした。このような新型の電界放出素子の稼動原理は従来の陰極線管（ＣＲＴ）と類似し、電子ビームの赤、緑、青三色蛍光粉を衝撃して発光させることによって画像形成または照明用途を実現しており、該種類の素子は明度、視角、応答時間、工作温度範囲、エネルギー消耗などの方面において共に潜在的な長所を有する。 Since the idea of an electron beam micro-type device based on field emission cathode arrays (FEAs) was submitted by Ken Shoulder in the 1960s, research to design and manufacture panel displays and light source elements using FEAs has generally generated tremendous interest. It was. The operating principle of such a new type of field emission device is similar to that of a conventional cathode ray tube (CRT), and realizes image formation or illumination applications by irradiating red, green and blue three-color fluorescent powders of an electron beam to emit light. These types of elements have potential advantages in terms of brightness, viewing angle, response time, working temperature range, energy consumption, and the like.
性能の優良な電界放出素子を製作することの重要な要因の１つは高性能蛍光粉の調製である。現在電界放出素子に採用される蛍光材料は主に従来の陰極線管及び投影型テレビキネスコープに用いられている硫化物系、酸化物系及び硫黄酸化物系蛍光粉である。硫化物及び硫黄酸化物系蛍光粉にとって、発光明度が比較的高く、且つある程度の導電性を有するが、ビックビーム電子ビームの衝撃下で分解しやすく、単体硫黄を放出して陰極ピンポイントを「ポイズン」し、且つその他の沈殿物を生成して蛍光粉の表面に被覆するため、蛍光粉の発光効率を低減し、電界放出素子の使用寿命を短縮した。酸化物蛍光粉は安定性がよいが、発光効率が高くなく、且つ材料のほとんどが絶縁体であるため、両者の性能は共に改善及び向上する必要がある。 One of the important factors in producing a field emission device with excellent performance is the preparation of high-performance fluorescent powder. Fluorescent materials currently used in field emission devices are mainly sulfide-based, oxide-based and sulfur oxide-based fluorescent powders used in conventional cathode ray tubes and projection television kinescopes. For sulfide and sulfur oxide-based fluorescent powders, the light emission brightness is relatively high and it has a certain degree of conductivity, but it is easily decomposed under the impact of a big beam electron beam, releasing single sulfur and reducing the cathode pinpoint. Since it “poisons” and other precipitates are generated and coated on the surface of the fluorescent powder, the luminous efficiency of the fluorescent powder is reduced and the service life of the field emission device is shortened. Although the oxide fluorescent powder has good stability, the luminous efficiency is not high, and most of the material is an insulator, so both performances need to be improved and improved.
これに鑑みて、本発明はＣｅ３＋、Ｔｂ３＋及びＡｇイオンがドーピングされた珪酸塩発光材料を提供し、該珪酸塩発光材料の安定性及び発光効率が高い。 In view of this, the present invention provides a silicate light-emitting material doped with Ce 3+ , Tb 3+ and Ag ions, and the stability and light emission efficiency of the silicate light-emitting material is high.
また、調製プロセスが簡単で、低コストの珪酸塩発光材料の調製方法を提供する。 Further, the present invention provides a method for preparing a silicate luminescent material with a simple preparation process and low cost.
本発明の技術的課題を解決する技術的手段は、
珪酸塩発光材料であって、その分子式がＬｎ２−ｘ−ｙＳｉＯ５：Ｃｅｘ,Ｔｂｙ,Ａｇｚであり、式中、ＬｎがＹ、Ｇｄ、Ｌａ、Ｌｕのうちの１種で、ｘ値の範囲が０＜ｘ≦０．０５、ｙ値の範囲が０．０１≦ｙ≦０．２５、ｚ値の範囲が０＜ｚ≦０．００５である。
Technical means for solving the technical problems of the present invention include:
A silicate luminescent material, its molecular formula Ln 2-x-y SiO 5 : Ce x, Tb y, a Ag z, wherein, Ln is Y, Gd, La, at one of Lu, The x value range is 0 <x ≦ 0.05, the y value range is 0.01 ≦ y ≦ 0.25, and the z value range is 0 <z ≦ 0.005.
また、珪酸塩発光材料の調製方法であって、前記方法は、
一般式Ｌｎ２−ｘ−ｙＳｉＯ５：Ｃｅｘ,Ｔｂｙ,Ａｇｚにおける相応する元素の化学計量比に基づいて、Ｌｎを源とする化合物と、Ｃｅを源とする化合物と、Ｔｂを源とする化合物と、Ａｇを源とする化合物と、シリカエーロゲルとを秤取し、式中、ＬｎがＹ、Ｇｄ、Ｌａ、及びＬｕのうちの１種であり、ｘ値の範囲が０＜ｘ≦０．０５、ｙ値の範囲が０．０１≦ｙ≦０．２５、ｚ値の範囲が０＜ｚ≦０．００５であるステップと、
シリカエーロゲルを、Ａｇを源とする化合物のアルコール溶液に溶解し、その後撹拌、乾燥、焼成を順に行って、Ａｇ含有のシリカエーロゲルを得るステップと、
秤取した前記Ｌｎを源とする化合物と、Ｃｅを源とする化合物と、Ｔｂを源とする化合物と、Ａｇ含有のシリカエーロゲルとを混合した後、還元雰囲気下で焼成を行い、一般式Ｌｎ２−ｘ−ｙＳｉＯ５：Ｃｅｘ,Ｔｂｙ,Ａｇｚである、前記珪酸塩発光材料を得るステップとを含む。
Also, a method for preparing a silicate luminescent material, the method comprising:
Formula Ln 2-x-y SiO 5 : Ce x, Tb y, based on the chemical metering ratio of the corresponding elements in the Ag z, source compound to sources of Ln, a compound that sourced from Ce, and Tb , A compound using Ag as a source, and a silica aerogel, Ln is one of Y, Gd, La, and Lu, and the range of the x value is 0 < a step in which x ≦ 0.05, a range of y value is 0.01 ≦ y ≦ 0.25, and a range of z value is 0 <z ≦ 0.005;
Dissolving silica aerogel in an alcohol solution of a compound based on Ag, followed by stirring, drying, and firing in order to obtain an Ag-containing silica airgel;
The weighed Ln source compound, Ce source compound, Tb source compound, and Ag-containing silica aerogel are mixed and fired in a reducing atmosphere. ln 2-x-y SiO 5 : a Ce x, Tb y, Ag z , and a step of obtaining the silicate luminescent material.
前記珪酸塩発光材料及びその調製方法において、該珪酸塩発光材料にはＣｅ３＋及びＴｂ３＋がドーピングされたため、電子ビームの励起下で暖かい白光を発射でき、また、該珪酸塩発光材料におけるＡｇ単体が珪酸塩発光材料の安定性及び発光効率を有効に向上し、該珪酸塩発光材料の調製方法において、まずＡｇ含有のシリカエーロゲルを調製し、さらにその他の組成と混合して且つ焼成を行うことによって、発光材料を得ることができる。それによって、調製プロセスを簡略化してコストを低減し、広範な生産への応用が期待される。 In the silicate luminescent material and the preparation method thereof, Ce 3+ and Tb 3+ are doped in the silicate luminescent material, so that warm white light can be emitted under excitation of an electron beam, and Ag alone in the silicate luminescent material Effectively improves the stability and luminous efficiency of the silicate luminescent material. In the method for preparing the silicate luminescent material, first, an Ag-containing silica aerogel is prepared, and further mixed with other compositions and fired. Thus, a light emitting material can be obtained. This simplifies the preparation process, reduces costs, and is expected to be applied to a wide range of production.
以下、図面及び実施例に合わせて、本発明に対してさらに説明する。
本発明の目的、技術的解決手段及び利点をより明白にするため、以下、図面及び実施例に合わせて、本発明に対してさらに詳細に説明する。理解すべきなのは、ここで説明する具体的な実施例は本発明を解釈するために用いられているのみであり、本発明を制限するものではない。 In order to make the objects, technical solutions and advantages of the present invention clearer, the present invention will be described in more detail with reference to the drawings and examples. It should be understood that the specific embodiments described herein are only used to interpret the present invention and are not intended to limit the present invention.
本発明の実施例の珪酸塩発光材料であって、その分子式がＬｎ２−ｘ−ｙＳｉＯ５：Ｃｅｘ,Ｔｂｙ,Ａｇｚであり、式中、ＬｎがＹ、Ｇｄ、Ｌａ、Ｌｕのうちの１種で、ｘ値の範囲が０＜ｘ≦０．０５、ｙ値の範囲が０．０１≦ｙ≦０．２５、ｚ値の範囲が０＜ｚ≦０．００５である。 A silicate luminescent materials of Examples of the present invention, its molecular formula Ln 2-x-y SiO 5 : a Ce x, Tb y, Ag z , wherein, Ln is Y, Gd, La, and Lu In one of them, the range of the x value is 0 <x ≦ 0.05, the range of the y value is 0.01 ≦ y ≦ 0.25, and the range of the z value is 0 <z ≦ 0.005.
前記ｘ値の範囲は０．００１≦ｘ≦０．０４が好ましく、ｙ値の範囲は０．０３≦ｙ≦０．２が好ましく、ｚ値の範囲は０．００００３≦ｚ≦０．００３が好ましい。 The x value range is preferably 0.001 ≦ x ≦ 0.04, the y value range is preferably 0.03 ≦ y ≦ 0.2, and the z value range is 0.00003 ≦ z ≦ 0.003. preferable.
前記珪酸塩発光材料にはＣｅ３＋及びＴｂ３＋がドーピングされたため、電子ビームの励起下で暖かい白光を発射でき、また、該珪酸塩発光材料におけるＡｇ単体が該珪酸塩発光材料の安定性及び発光効率が有効に向上した。この珪酸塩発光材料における各元素の割合を適当に調整し、例えば、当該珪酸塩発光材料の分子式Ｌｎ２−ｘ−ｙＳｉＯ５：Ｃｅｘ、Ｔｂｙ、Ａｇｚにおけるｘ値の範囲は０．００１≦ｘ≦０．０４が好ましく、ｙ値の範囲は０．０３≦ｙ≦０．２が好ましく、ｚ値の範囲は０．００００３≦ｚ≦０．００３が好ましく、該珪酸塩発光材料の安定性及び発光効率をさらに向上させることができる。Ｌｎが該珪酸塩発光材料の重要な組成元素であり、発光材料の分子構造を構成する役割を果たし、Ｙ、Ｇｄ、Ｌａ、Ｌｕの性質が近似しているため相互に代わって、発光材料の分子構造を変更しなくてもよい。 Since the silicate luminescent material is doped with Ce 3+ and Tb 3+ , warm white light can be emitted under excitation of an electron beam, and Ag alone in the silicate luminescent material is stable and luminescent of the silicate luminescent material. Efficiency is improved effectively. The proportion of each element in the silicate luminescent material suitably adjusted, for example, the silicate luminescent materials of molecular formula Ln 2-x-y SiO 5 : Ce x, Tb y, a range of x values in Ag z is 0. 001 ≦ x ≦ 0.04 is preferable, the range of y value is preferably 0.03 ≦ y ≦ 0.2, and the range of z value is preferably 0.00003 ≦ z ≦ 0.003. Stability and luminous efficiency can be further improved. Ln is an important composition element of the silicate luminescent material, plays a role in constituting the molecular structure of the luminescent material, and the properties of Y, Gd, La, and Lu are close to each other. It is not necessary to change the molecular structure.
また、珪酸塩発光材料の調製方法であって、図３に示すように、その調製プロセスの流れは、
一般式Ｌｎ２−ｘ−ｙＳｉＯ５：Ｃｅｘ、Ｔｂｙ、Ａｇｚにおける相応する元素の化学計量比に基づいて、Ｌｎを源とする化合物と、Ｃｅを源とする化合物と、Ｔｂを源とする化合物と、Ａｇを源とする化合物と、シリカエーロゲルとを秤取し、式中、ＬｎがＹ、Ｇｄ、Ｌａ、及びＬｕのうちの１種であり、ｘ値の範囲が０＜ｘ≦０．０５、ｙ値の範囲が０．０１≦ｙ≦０．２５、ｚ値の範囲が０＜ｚ≦０．００５であるステップＳ１と、
Ａｇを源とする化合物のアルコール溶液にシリカエーロゲルを溶解し、その後撹拌、乾燥、焼成を順に行って、Ａｇ含有のシリカエーロゲルを得るステップＳ２と、
秤取した前記Ｌｎを源とする化合物と、Ｃｅを源とする化合物と、Ｔｂを源とする化合物と、Ａｇ含有のシリカエーロゲルとを混合した後、還元雰囲気下で焼成を行い、一般式Ｌｎ２−ｘ−ｙＳｉＯ５：Ｃｅｘ、Ｔｂｙ、Ａｇｚである、前記珪酸塩発光材料を得るステップＳ３とを含む。
Also, a method for preparing a silicate luminescent material, as shown in FIG.
Formula Ln 2-x-y SiO 5 : Ce x, Tb y, based on the chemical metering ratio of the corresponding elements in the Ag z, source compound to sources of Ln, a compound that sourced from Ce, and Tb , A compound using Ag as a source, and a silica aerogel, Ln is one of Y, Gd, La, and Lu, and the range of the x value is 0 < Step S1 where x ≦ 0.05, the y value range is 0.01 ≦ y ≦ 0.25, and the z value range is 0 <z ≦ 0.005;
Step S2 in which silica aerogel is dissolved in an alcohol solution of a compound using Ag as a source, followed by stirring, drying, and firing in this order to obtain an Ag-containing silica airgel;
The weighed Ln source compound, Ce source compound, Tb source compound, and Ag-containing silica aerogel are mixed and fired in a reducing atmosphere. ln 2-x-y SiO 5 : Ce x, Tb y, a Ag z, and a step S3 to obtain the silicate luminescent material.
前記珪酸塩発光材料の調製方法のステップＳ１において、前記Ｌｎを源とする化合物はＬｎの酸化物、硝酸塩、炭酸塩、及びシュウ酸塩のうちの少なくとも１種が好ましく、Ｃｅを源とする化合物はＣｅの酸化物、硝酸塩、炭酸塩、及びシュウ酸塩のうちの少なくとも１種が好ましく、Ｔｂを源とする化合物はＴｂの酸化物、硝酸塩、炭酸塩、及びシュウ酸塩のうちの少なくとも１種が好ましく、前記Ａｇを源とする化合物はＡｇの硝酸塩または／及びナノＡｇコロイド粒子が好ましく、シリカエーロゲルに使用されるエーロゲルは、直接市販されており、例えば「納諾高科股▲ふん▼有限公司」の製品であってもよい。 In step S1 of the method for preparing a silicate luminescent material, the compound having Ln as a source is preferably at least one of Ln oxide, nitrate, carbonate, and oxalate, and having Ce as a source. Is preferably at least one of Ce oxides, nitrates, carbonates and oxalates, and the Tb source compound is at least one of Tb oxides, nitrates, carbonates and oxalates. Species are preferred, and the Ag-based compound is preferably Ag nitrate or / and nano-Ag colloidal particles, and the aerogel used for the silica aerogel is directly commercially available. Co., Ltd.'s product.
前記珪酸塩発光材料の調製方法のステップＳ２において、前記撹拌過程が５０℃〜７５℃、超音波条件下で行われ、且つ撹拌時間が０．５時間〜３時間であり、超音波の目的はシリカエーロゲルと、Ａｇを源とする化合物とをアルコール溶液において十分混合させることであり、超音波処理の時間は１０分間が好ましいがこれに限定せず、前記乾燥過程が６０℃〜１５０℃下で行われ、前記焼成過程が６００℃〜１０００℃下で行われる。 In step S2 of the method for preparing the silicate luminescent material, the stirring process is performed at 50 ° C. to 75 ° C. under ultrasonic conditions, and the stirring time is 0.5 hours to 3 hours. Silica airgel and a compound based on Ag are sufficiently mixed in an alcohol solution, and the time of ultrasonic treatment is preferably 10 minutes, but is not limited thereto, and the drying process is performed at 60 ° C. to 150 ° C. And the firing process is performed at 600 ° C. to 1000 ° C.
前記ステップＳ２において、選ばれたシリカエーロゲルの孔径が２０ｎｍ〜１００ｎｍであり、気孔率は９２％〜９８％が好ましく、前記焼成は６００℃〜１３００℃下で０．５時間〜３時間熱処理を行うことが好ましく、前記アルコール溶液はエタノール溶液が好ましいがこれに限定せず、Ａｇを源とする化合物のアルコール溶液における濃度は１．５×１０−５〜１．２５×１０−３ｍｏｌ／Ｌが好ましい。 In the step S2, the selected silica airgel has a pore diameter of 20 nm to 100 nm, preferably a porosity of 92% to 98%, and the calcination is heat treatment at 600 ° C. to 1300 ° C. for 0.5 hour to 3 hours. The alcohol solution is preferably an ethanol solution, but is not limited thereto, and the concentration of the compound using Ag as a source in the alcohol solution is 1.5 × 10 −5 to 1.25 × 10 −3 mol / L. Is preferred.
前記珪酸塩発光材料の調製方法のステップＳ３において、前記還元雰囲気下で焼成する焼成温度は１３００℃〜１６００℃が好ましく、時間は１時間〜８時間が好ましく、前記還元雰囲気はＮ２とＨ２との混合還元雰囲気、ＣＯ還元雰囲気、Ｈ２還元雰囲気のうちの１種が好ましく、Ｎ２とＨ２との還元雰囲気におけるＮ２とＨ２との体積比は９５：５が好ましいがこれに限定せず、該還元雰囲気に焼成する目的は、燃焼過程に生成された＋４価Ｃｅ、Ｔｂイオン及びＡｇイオンを＋３価Ｃｅ、Ｔｂイオン及びＡｇ単体に還元し、それによってＬｎ２−ｘ−ｙＳｉＯ５：Ｃｅｘ,Ｔｂｙ,Ａｇｚ化合物に生成し、Ｌｎ２−ｘ−ｙＳｉＯ５：Ｃｅｘ,Ｔｂｙ,Ａｇｚの発光性能を有効に保証した。還元雰囲気は、体積比に基づいて還元性ガスの含有量が１０％より低い混合ガスを指す。 In step S3 of the method for preparing the silicate luminescent material, the firing temperature for firing in the reducing atmosphere is preferably 1300 ° C to 1600 ° C, the time is preferably 1 hour to 8 hours, and the reducing atmosphere is N 2 and H 2. mixing a reducing atmosphere of, CO reducing atmosphere, one preferably of the H 2 reducing atmosphere, the volume ratio of N 2 and H 2 in the reducing atmosphere of N 2 and H 2 is 95: in but 5 are preferred which Without limitation, the purpose of firing in the reducing atmosphere is to reduce +4 valent Ce, Tb ions and Ag ions generated in the combustion process to +3 valent Ce, Tb ions and Ag alone, thereby producing Ln 2-xy. SiO 5: Cex, generates Tby, the Agz compounds, Ln 2-x-y SiO 5: Cex, Tby, and effectively guarantee the emission performance of Agz. The reducing atmosphere refers to a mixed gas having a reducing gas content lower than 10% based on a volume ratio.
該珪酸塩発光材料の調製方法において、高温固相法を使用して、まずＡｇ含有のシリカエーロゲルを調製し、さらにその他の組成と混合して且つ焼成を行うことによって、発光材料を得ることができ、それによって、調製プロセスを簡略化してコストを低くし、広範な生産応用が期待される。 In the method for preparing the silicate luminescent material, first, an Ag-containing silica aerogel is prepared using a high-temperature solid-phase method, and further mixed with another composition and fired to obtain a luminescent material. Thereby simplifying the preparation process, lowering costs, and widespread production applications.
以下、複数の実施例を通じて例を挙げて珪酸塩発光材料の異なる組成及びその調製方法、並びにその性能などを説明する。 Hereinafter, different compositions of silicate light-emitting materials, their preparation methods, their performance, etc. will be described by way of examples.
実施例１
高温固相法によってＹ１．９８９ＳｉＯ５：Ｃｅ０．００１、Ｔｂ０．０１、Ａｇ０．００００３を調製する
まずシリカエーロゲル０．３ｇを秤取して、ＡｇＮＯ３を１．５×１０−５ｍｏｌ/Ｌ含有する１０ｍｌのエタノール溶液に溶解し、５０℃下で３時間撹拌する。その後１０分間超音波処理し、さらに６０℃で乾燥し、乾燥した後のサンプルを研磨して均一にし、６００℃下で４時間事前焼成し、Ａｇ含有のシリカエーロゲルを得る。Ｙ２(ＣＯ３)３を１．４２０１ｇ、Ｃｅ２(ＣＯ３)３を０．０００９ｇ、Ｔｂ２(ＣＯ３)３を０．００９９ｇ及びＡｇ含有のシリカエーロゲル０．２４０４ｇを秤取して均一に混合し、さらに９５％Ｎ２＋５％Ｈ２還元雰囲気において１３００℃で８時間保温焼結し、得た生成物を室温まで冷却して、Ｙ１．９８９ＳｉＯ５：Ｃｅ０．００１、Ｔｂ０．０１、Ａｇ０．００００３発光材料を得て、電子ビームの励起下で暖かい白光を発射する。
Example 1
Preparation of Y 1.989 SiO 5 : Ce 0.001 , Tb 0.01 , Ag 0.00003 by high-temperature solid phase method First, 0.3 g of silica airgel is weighed and AgNO 3 is added to 1.5 × 10 6. Dissolve in 10 ml ethanol solution containing -5 mol / L and stir at 50 ° C. for 3 hours. Then, it is sonicated for 10 minutes, further dried at 60 ° C., the dried sample is polished and made uniform, and pre-baked at 600 ° C. for 4 hours to obtain an Ag-containing silica airgel. Weigh 1.4201 g of Y 2 (CO 3 ) 3 , 0.0009 g of Ce 2 (CO 3 ) 3 , 0.0099 g of Tb 2 (CO 3 ) 3 and 0.2404 g of Ag-containing silica airgel. Mix uniformly, and further heat-sinter at 1300 ° C. for 8 hours in a 95% N 2 + 5% H 2 reducing atmosphere. The resulting product is cooled to room temperature, and Y 1.989 SiO 5 : Ce 0.001 , A Tb 0.01 , Ag 0.00003 luminescent material is obtained and emits warm white light under the excitation of an electron beam.
実施例２
高温固相法によってＬａ１．９６２ＳｉＯ５：Ｃｅ０．００８、Ｔｂ０．０３、Ａｇ０．００００７を調製する
まずシリカエーロゲル０．４ｇを秤取して、２０ｍｌ、ナノＡｇコロイド粒子２．３４５×１０−５ｍｏｌ/Ｌ含有のエタノール溶液に溶解し、６０℃下で２時間撹拌し、その後１０分間超音波処理し、さらに８０℃で乾燥し、乾燥した後のサンプルを研磨して均一にし、８００℃下で２時間事前焼成し、Ａｇ含有のシリカエーロゲルを得る。Ｌａ２Ｏ３を１．２７８４ｇ、ＣｅＯ２を０．００５５ｇ、Ｔｂ４Ｏ７を０．０２２４ｇ及びＡｇ含有のシリカエーロゲル０．２４０４ｇを秤取して均一に混合し、さらに９５％Ｎ２＋５％Ｈ２還元雰囲気において１４５０℃で４時間保温焼結し、得た生成物を室温まで冷却して、Ｌａ１．９６２ＳｉＯ５：Ｃｅ０．００８、Ｔｂ０．０３、Ａｇ０．００００７発光材料を得て、電子ビームの励起下で暖かい白光を発射する。
Example 2
Hot solid phase method by La 1.962 SiO 5: Ce 0.008, Tb 0.03, and weighed first silica airgel 0.4g preparing Ag 0.00007, 20 ml, nano Ag colloidal particles 2. Dissolve in an ethanol solution containing 345 × 10 −5 mol / L, stir at 60 ° C. for 2 hours, then sonicate for 10 minutes, further dry at 80 ° C., and polish the sample after drying to make uniform And pre-baked at 800 ° C. for 2 hours to obtain an Ag-containing silica airgel. 1.2784 g La 2 O 3 , 0.0055 g CeO 2 , 0.0224 g Tb 4 O 7 and 0.2404 g Ag-containing silica airgel were weighed and mixed uniformly, and further 95% N 2 +5 Sintering is carried out at 1450 ° C. for 4 hours in a% H 2 reducing atmosphere, and the obtained product is cooled to room temperature to obtain La 1.962 SiO 5 : Ce 0.008 , Tb 0.03 , Ag 0.00007 luminescent material And emit warm white light under the excitation of an electron beam.
実施例３
高温固相法によってＧｄ１．７６ＳｉＯ５：Ｃｅ０．０４、Ｔｂ０．２、Ａｇ０．００１を調製する
まず、シリカエーロゲル１．０ｇを秤取して、３０ｍｌ、ナノＡｇコロイド粒子５．４３×１０−４ｍｏｌ/Ｌ含有のメタノール溶液に溶解し、７０℃下で０．５時間撹拌し、その後１０分間超音波処理し、さらに１５０℃で乾燥し、乾燥した後のサンプルを研磨して均一にし、１０００℃下で０．５時間事前焼成し、Ａｇ含有のシリカエーロゲルを得る。Ｇｄ(ＮＯ３)３を２．４１６８ｇ、Ｃｅ(ＮＯ３)３を０．０５２１ｇ、Ｔｂ(ＮＯ３)３を０．２７６０ｇ及びＡｇ含有のシリカエーロゲル０．２４０４ｇを秤取して均一に混合し、さらにＣＯの還元雰囲気において１６００℃で１時間保温焼結し、得た生成物を室温まで冷却して、Ｇｄ１．７６ＳｉＯ５：Ｃｅ０．０４、Ｔｂ０．２、Ａｇ０．００１発光材料を得て、電子ビームの励起下で暖かい白光を発射する。
Example 3
First, Gd 1.76 SiO 5 : Ce 0.04 , Tb 0.2 , Ag 0.001 is prepared by a high-temperature solid phase method. First, 1.0 g of silica airgel is weighed, and 30 ml, nano Ag colloidal particles 5 Dissolve in a methanol solution containing .43 × 10 −4 mol / L, stir at 70 ° C. for 0.5 hour, then sonicate for 10 minutes, further dry at 150 ° C., and polish the sample after drying And pre-baked at 1000 ° C. for 0.5 hour to obtain an Ag-containing silica airgel. Gd (NO 3 ) 3 of 2.4168 g, Ce (NO 3 ) 3 of 0.0521 g, Tb (NO 3 ) 3 of 0.2760 g and Ag-containing silica aerogel 0.2404 g were weighed and mixed uniformly. Further, the mixture was heat-sintered at 1600 ° C. for 1 hour in a reducing atmosphere of CO, and the obtained product was cooled to room temperature. Gd 1.76 SiO 5 : Ce 0.04 , Tb 0.2 , Ag 0.001 A luminescent material is obtained and warm white light is emitted under the excitation of an electron beam.
実施例４
高温固相法によってＹ１．８９ＳｉＯ５：Ｃｅ０．０１、Ｔｂ０．１、Ａｇ０．０００７を調製する
まずシリカエーロゲル０．４ｇを秤取して、１５ｍｌ、ナノＡｇコロイド粒子３．１２６６×１０−４ｍｏｌ/Ｌ含有のエタノール溶液に溶解し、６０℃下で１．５時間撹拌し、その後１０分間超音波処理し、さらに７０℃で乾燥し、乾燥した後のサンプルを研磨して均一にし、８００℃下で２時間事前焼成し、Ａｇ含有のシリカエーロゲルを得る。Ｙ２Ｏ３を０．８５３５ｇ、ＣｅＯ２を０．００５５ｇ、Ｔｂ４Ｏ７を０．０７４７ｇ、及び焼成後のシリカエーロゲル０．２４０４ｇを秤取して均一に混合し、さらに９５％Ｎ２＋５％Ｈ２還元雰囲気において１５００℃で４時間保温焼結し、得た生成物を室温まで冷却して、Ｙ１．８９ＳｉＯ５：Ｃｅ０．０１、Ｔｂ０．１、Ａｇ０．０００７発光材料を得て、電子ビームの励起下で暖かい白光を発射する。図１は、Ｙ１．８９ＳｉＯ５：Ｃｅ０．０１、Ｔｂ０．１蛍光粉と本実施例により調製された珪酸塩発光材料との陰極線発光スペクトル対比図で、図１における１０が本実施例により調製された珪酸塩発光材料を指し、図における１１がＹ１．８９ＳｉＯ５：Ｃｅ０．０１、Ｔｂ０．１蛍光粉を指す。図１に示すように、本実施例の発光材料は３６０ｎｍ〜５００ｎｍ内に強いブロードバンド発射スペクトルを有し、且つ５４４ｎｍのところに１つのナローバンドピックを有し、５４４ｎｍのところの発光強度がＹ１．８９ＳｉＯ５：Ｃｅ０．０１、Ｔｂ０．１の発光強度より高く、本実施例により調製された発光材料の発光強度はＡｇのドーピングされなかったＹ１．８９ＳｉＯ５：Ｃｅ０．０１、Ｔｂ０．１蛍光粉より３８％も超えていて、本実施例の発光材料は安定性がよく、発光効率が高い特徴を有する。
Example 4
2. Prepare Y 1.89 SiO 5 : Ce 0.01 , Tb 0.1 , Ag 0.0007 by high-temperature solid phase method First, 0.4 g of silica airgel is weighed and 15 ml of nano Ag colloidal particles. Dissolve in an ethanol solution containing 1266 × 10 −4 mol / L, stir at 60 ° C. for 1.5 hours, then sonicate for 10 minutes, further dry at 70 ° C., and polish the sample after drying. And pre-baked at 800 ° C. for 2 hours to obtain an Ag-containing silica airgel. 0.8535 g of Y 2 O 3 , 0.0055 g of CeO 2 , 0.0747 g of Tb 4 O 7, and 0.2404 g of the fired silica airgel were weighed and mixed uniformly, and further 95% N 2 Incubation was performed at 1500 ° C. for 4 hours in a + 5% H 2 reducing atmosphere, and the obtained product was cooled to room temperature. Y 1.89 SiO 5 : Ce 0.01 , Tb 0.1 , Ag 0.0007 light emission Get material and emit warm white light under the excitation of electron beam. FIG. 1 is a cathode ray emission spectrum comparison diagram of Y 1.89 SiO 5 : Ce 0.01 , Tb 0.1 fluorescent powder and a silicate luminescent material prepared according to this example, where 10 in FIG. It refers to a silicate luminescent material prepared by example, and 11 in the figure refers to Y 1.89 SiO 5 : Ce 0.01 , Tb 0.1 fluorescent powder. As shown in FIG. 1, the luminescent material of this example has a strong broadband emission spectrum in the range of 360 nm to 500 nm, one narrow band pick at 544 nm, and an emission intensity at 544 nm of Y 1. The emission intensity of the light emitting material prepared according to this example is higher than the emission intensity of 89 SiO 5 : Ce 0.01 , Tb 0.1 , and Y 1.89 SiO 5 : Ce 0.01 not doped with Ag. Tb is more than 38% of 0.1 fluorescent powder, and the light-emitting material of this example is characterized by good stability and high light emission efficiency.
実施例５
高温固相法によってＬｕ１．７３ＳｉＯ５：Ｃｅ０．０２、Ｔｂ０．２５、Ａｇ０．００３を調製する
まず、シリカエーロゲル０．３５ｇを秤取して、２５ｍｌ、ＡｇＮＯ３を７．０８×１０−４ｍｏｌ/Ｌ含有するプロパノール溶液に溶解し、６５℃下で１．５時間撹拌し、その後１０分間超音波処理し、さらに１２０℃で乾燥し、乾燥した後のサンプルを研磨して均一にし、１０００℃下で２時間事前焼成し、Ａｇ含有のシリカエーロゲルを得る。Ｌｕ２(Ｃ２Ｏ４)３を２．１２４４ｇ、Ｃｅ２(ＣＯ３)３を０．０１８４ｇ、Ｔｂ２(Ｃ２Ｏ４)３を０．２９０９ｇ及び焼成後のシリカエーロゲル０．２４０４ｇを秤取して均一に混合し、さらにＨ２還元雰囲気において１４００℃で６時間保温焼結し、得た生成物を室温まで冷却して、Ｌｕ１．７３ＳｉＯ５：Ｃｅ０．０２、Ｔｂ０．２５、Ａｇ０．００３発光材料を得て、電子ビームの励起下で暖かい白光を発射する。
Example 5
Lu 1.73 SiO 5 : Ce 0.02 , Tb 0.25 , Ag 0.003 are prepared by a high-temperature solid-phase method. First, 0.35 g of silica airgel is weighed and 25 ml of AgNO 3 is added. The sample was dissolved in a propanol solution containing 08 × 10 −4 mol / L, stirred at 65 ° C. for 1.5 hours, then sonicated for 10 minutes, further dried at 120 ° C., and the dried sample was polished. And pre-baked at 1000 ° C. for 2 hours to obtain an Ag-containing silica airgel. 2.1244 g of Lu 2 (C 2 O 4 ) 3 , 0.0184 g of Ce 2 (CO 3 ) 3 , 0.2909 g of Tb 2 (C 2 O 4 ) 3 and 0.2404 g of silica aerogel after firing Weighing and mixing uniformly, and further heat-sintered at 1400 ° C. for 6 hours in an H 2 reducing atmosphere, and the resulting product was cooled to room temperature to obtain Lu 1.73 SiO 5 : Ce 0.02 , Tb 0. .25 , Ag 0.003 luminescent material is obtained and emits warm white light under excitation of electron beam.
実施例６
高温固相法によってＧｄ１．９ＳｉＯ５：Ｃｅ０．０５、Ｔｂ０．０５、Ａｇ０．００５を調製する
まず、シリカエーロゲル０．３ｇを秤取して、ＡｇＮＯ３を１．２５×１０−３ｍｏｌ/Ｌ含有する２０ｍｌのエタノール溶液に溶解し、６０℃下で２時間撹拌する。その後１０分間超音波処理し、さらに１００℃で乾燥し、乾燥した後のサンプルを研磨して均一にし、８００℃下で２時間事前焼成し、Ａｇ含有のシリカエーロゲルを得る。Ｇｄ２(Ｃ２Ｏ４)３を２．１９８３ｇ、Ｃｅ２(Ｃ２Ｏ４)３を０．０５４０ｇ、Ｔｂ２(Ｃ２Ｏ４)３を０．０５８２ｇ及び焼成後のシリカエーロゲル０．２４０４ｇを秤取して均一に混合し、さらに９５％Ｎ２＋５％Ｈ２還元雰囲気において１４５０℃で４時間保温焼結し、得た生成物を室温まで冷却して、Ｇｄ１．９ＳｉＯ５：Ｃｅ０．０５、Ｔｂ０．０５、Ａｇ０．００５発光材料を得て、電子ビームの励起下で暖かい白光を発射する。
Example 6
Gd 1.9 SiO 5 : Ce 0.05 , Tb 0.05 , Ag 0.005 are prepared by a high temperature solid phase method. First, 0.3 g of silica airgel is weighed and AgNO 3 is added to 1.25 ×. Dissolve in 20 ml of ethanol solution containing 10 −3 mol / L and stir at 60 ° C. for 2 hours. Then, it is sonicated for 10 minutes, further dried at 100 ° C., the dried sample is polished and made uniform, and pre-baked at 800 ° C. for 2 hours to obtain an Ag-containing silica airgel. 2.9883 g of Gd 2 (C 2 O 4 ) 3 , 0.0540 g of Ce 2 (C 2 O 4 ) 3 , 0.0582 g of Tb 2 (C 2 O 4 ) 3 , and silica airgel 0. 2404 g was weighed out and mixed uniformly, and further sintered at 1450 ° C. for 4 hours in a reducing atmosphere of 95% N 2 + 5% H 2. The obtained product was cooled to room temperature, and Gd 1.9 SiO 5 : Ce 0.05 , Tb 0.05 , Ag 0.005 luminescent material is obtained and warm white light is emitted under excitation of electron beam.
実施例７
高温固相法によってＹ１．８９ＳｉＯ５：Ｃｅ０．０１、Ｔｂ０．１、Ａｇ０．０００４を調製する
まずシリカエーロゲル０．２８ｇを秤取して、ナノＡｇコロイド粒子を１．２２６６×１０−４ｍｏｌ/Ｌ含有する１５ｍｌのエタノール溶液に溶解し、６０℃下で２時間撹拌し、その後１０分間超音波処理し、さらに７０℃で乾燥し、乾燥した後のサンプルを研磨して均一にし、９００℃下で２時間事前焼成し、Ａｇ含有のシリカエーロゲルを得る。Ｙ２Ｏ３を０．８５３５ｇ、ＣｅＯ２を０．００５５ｇ、Ｔｂ４Ｏ７を０．０７４７ｇ、及びＡｇ含有のシリカエーロゲル０．２４０４ｇを秤取して均一に混合し、さらに９５％Ｎ２＋５％Ｈ２還元雰囲気において１４５０℃で４時間保温焼結し、得た生成物を室温まで冷却して、Ｙ１．８９ＳｉＯ５：Ｃｅ０．０１、Ｔｂ０．１、Ａｇ０．０００４発光材料を得て、電子ビームの励起下で暖かい白光を発射する。該Ｙ１．８９ＳｉＯ５：Ｃｅ０．０１、Ｔｂ０．１、Ａｇ０．０００４珪酸塩発光材料の５ＫＶ加速電圧の励起下の陰極線発光スペクトルを図２に示す。図２から分かるように、本実施例の発光材料は、３６０ｎｍ〜５００ｎｍ内に強いブロードバンド発射スペクトルを有し、且つ５４４ｎｍのところに１つのナローバンドピックを有して、これは実施例４により調製された珪酸塩発光材料の性能と非常に類似していて、それにより、本発明実施例の珪酸塩発光材料の性能が安定であることを示した。本実施例及び実施例４において、発光スペクトルは、共に５ＫＶ加速電圧の陰極線の励起下で、島津ＲＦ−５３０１ＰＣスペクトル装置を検出器として用いて分析して得たものである。
Example 7
Preparation of Y 1.89 SiO 5 : Ce 0.01 , Tb 0.1 , Ag 0.0004 by high-temperature solid phase method First, 0.28 g of silica airgel is weighed, and nano-Ag colloidal particles are added to 1.2266. Dissolve in 15 ml ethanol solution containing × 10 -4 mol / L, stir at 60 ° C for 2 hours, then sonicate for 10 minutes, further dry at 70 ° C, polish the sample after drying Uniform and pre-baked at 900 ° C. for 2 hours to obtain an Ag-containing silica aerogel. 0.8535 g of Y 2 O 3 , 0.0055 g of CeO 2 , 0.0747 g of Tb 4 O 7, and 0.2404 g of Ag-containing silica airgel were weighed and mixed uniformly, and further 95% N 2 Incubate at 1450 ° C. for 4 hours in a + 5% H 2 reducing atmosphere, cool the resulting product to room temperature, and emit Y 1.89 SiO 5 : Ce 0.01 , Tb 0.1 , Ag 0.0004 Get material and emit warm white light under the excitation of electron beam. FIG. 2 shows a cathode ray emission spectrum of the Y 1.89 SiO 5 : Ce 0.01 , Tb 0.1 , Ag 0.0004 silicate luminescent material under excitation with a 5 KV acceleration voltage. As can be seen from FIG. 2, the luminescent material of this example has a strong broadband emission spectrum within 360-500 nm and one narrow band pick at 544 nm, which is prepared according to Example 4. The performance of the silicate luminescent material was very similar to that of the silicate luminescent material, indicating that the performance of the silicate luminescent material of the examples of the present invention was stable. In this example and Example 4, the emission spectra were both obtained by analysis using a Shimadzu RF-5301PC spectrum device as a detector under the excitation of a cathode ray of 5 KV acceleration voltage.
以上、説明した実施例は本発明の好適な実施例にすぎず、本発明を制限するものではない。本発明の主旨及び原則内に行われたいずれの修正、等価の変更及び改良等は、すべて本発明の保護範囲内に含まれるべきである。 The embodiments described above are merely preferred embodiments of the present invention and do not limit the present invention. Any modifications, equivalent changes and improvements made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
分子式がＬｎ２−ｘ−ｙＳｉＯ５：Ｃｅｘ、Ｔｂｙ、Ａｇｚであり、式中、ＬｎがＹ、Ｇｄ、Ｌａ、Ｌｕのうちの１種で、ｘ値の範囲が０．００８＜ｘ≦０．０５、ｙ値の範囲が０．０１≦ｙ≦０．２５、ｚ値の範囲が０＜ｚ≦０．００５であり、
前記珪酸塩発光材料は、電子ビームの励起下で白光を発射する、珪酸塩発光材料。 A silicate luminescent material,
Molecular formula Ln 2-x-y SiO 5 : a Ce x, Tb y, Ag z , wherein, Ln is Y, Gd, La, at one of Lu, the range of x values 0.008 < x ≦ 0.05, the range of y values is 0.01 ≦ y ≦ 0.25, Ri range of z values 0 <z ≦ 0.005 der,
The silicate luminescent material is a silicate luminescent material that emits white light under excitation of an electron beam .
一般式Ｌｎ２−ｘ−ｙＳｉＯ５：Ｃｅｘ、Ｔｂｙ、Ａｇｚにおける相応する元素の化学計量比に基づいて、Ｌｎを源とする化合物と、Ｃｅを源とする化合物と、Ｔｂを源とする化合物と、Ａｇを源とする化合物と、シリカエーロゲルとを秤取し、式中、ＬｎがＹ、Ｇｄ、Ｌａ、及びＬｕのうちの１種であり、ｘ値の範囲が０．００８＜ｘ≦０．０５、ｙ値の範囲が０．０１≦ｙ≦０．２５、ｚ値の範囲が０＜ｚ≦０．００５であるステップと、
Ａｇを源とする化合物のアルコール溶液にシリカエーロゲルを溶解し、その後撹拌、乾燥、焼成を順に行って、Ａｇ含有のシリカエーロゲルを得るステップと、
秤取した前記Ｌｎを源とする化合物と、Ｃｅを源とする化合物と、Ｔｂを源とする化合物と、Ａｇ含有のシリカエーロゲルとを混合した後、還元雰囲気下で焼成を行い、一般式Ｌｎ２−ｘ−ｙＳｉＯ５：Ｃｅｘ、Ｔｂｙ、Ａｇｚである、前記珪酸塩発光材料を得るステップと、
を含み、
前記珪酸塩発光材料は、電子ビームの励起下で白光を発射する、珪酸塩発光材料の調製方法。 A method for preparing a silicate luminescent material, comprising:
Formula Ln 2-x-y SiO 5 : Ce x, Tb y, based on the chemical metering ratio of the corresponding elements in the Ag z, source compound to sources of Ln, a compound that sourced from Ce, and Tb , A compound using Ag as a source, and a silica aerogel, Ln is one of Y, Gd, La, and Lu, and the range of the x value is 0.8. 008 <x ≦ 0.05, the y value range is 0.01 ≦ y ≦ 0.25, and the z value range is 0 <z ≦ 0.005;
Dissolving silica aerogel in an alcohol solution of a compound using Ag as a source, and then stirring, drying, and firing in order to obtain an Ag-containing silica aerogel;
The weighed Ln source compound, Ce source compound, Tb source compound, and Ag-containing silica aerogel are mixed and fired in a reducing atmosphere. ln 2-x-y SiO 5 : a Ce x, Tb y, Ag z , and obtaining the silicate luminescent material,
Only including,
The method for preparing a silicate luminescent material, wherein the silicate luminescent material emits white light under excitation of an electron beam .
前記Ｃｅを源とする化合物がＣｅの酸化物、硝酸塩、炭酸塩、及びシュウ酸塩のうちの少なくとも１種、
前記Ｔｂを源とする化合物がＴｂの酸化物、硝酸塩、炭酸塩、及びシュウ酸塩のうちの少なくとも１種、
前記Ａｇを源とする化合物がＡｇの硝酸塩及び／またはナノＡｇコロイド粒子であることを特徴とする、請求項３に記載の珪酸塩発光材料の調製方法。 The Ln-based compound is at least one of an oxide, nitrate, carbonate, and oxalate of Ln,
The Ce-based compound is at least one of Ce oxide, nitrate, carbonate, and oxalate;
The Tb source compound is at least one of Tb oxide, nitrate, carbonate and oxalate;
The method for preparing a silicate luminescent material according to claim 3, wherein the Ag-based compound is Ag nitrate and / or nano Ag colloidal particles.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/CN2010/075246 WO2012009844A1 (en) | 2010-07-19 | 2010-07-19 | Luminescent material of silicate and preparing method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2013533910A JP2013533910A (en) | 2013-08-29 |
| JP5655141B2 true JP5655141B2 (en) | 2015-01-14 |
Family
ID=45496437
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2013516956A Active JP5655141B2 (en) | 2010-07-19 | 2010-07-19 | Silicate luminescent material and preparation method thereof |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US20130075659A1 (en) |
| EP (1) | EP2597133B1 (en) |
| JP (1) | JP5655141B2 (en) |
| CN (1) | CN102933687A (en) |
| WO (1) | WO2012009844A1 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9605202B2 (en) | 2012-03-29 | 2017-03-28 | Ocean's King Lighting Science & Technology Co., Ltd. | Silicate luminescent materials doped with metal nano particles and preparation methods therefor |
| CN104755587A (en) * | 2012-10-31 | 2015-07-01 | 海洋王照明科技股份有限公司 | Aluminate luminescent material and preparation method therefor |
| JP6034503B2 (en) * | 2012-10-31 | 2016-11-30 | オーシャンズ キング ライティング サイエンスアンドテクノロジー カンパニー リミテッド | Silicate luminescent material and method for producing the same |
| JP5965551B2 (en) * | 2012-10-31 | 2016-08-10 | オーシャンズ キング ライティング サイエンスアンドテクノロジー カンパニー リミテッド | Silicate luminescent material and method for producing the same |
| CN105112045A (en) * | 2015-08-20 | 2015-12-02 | 桂林市环境监测中心站 | Luminescent material containing dielectric layer and metal nanoparticles and preparation method therefor |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5927787B2 (en) * | 1977-04-13 | 1984-07-07 | 株式会社東芝 | UV-excited phosphor |
| FR2634028B1 (en) * | 1988-07-06 | 1994-07-22 | Commissariat Energie Atomique | LANTHANIDE SILICATE MONOCRYSTALS FOR USE AS SCINTILLATORS FOR DETECTION OF X-RAYS AND GAMMA |
| US6278832B1 (en) * | 1998-01-12 | 2001-08-21 | Tasr Limited | Scintillating substance and scintillating wave-guide element |
| DE10049803A1 (en) * | 2000-10-09 | 2002-04-18 | Bayer Ag | Composite particles used e.g. for pigmenting paint or plastics comprise unagglomerated primary pigment particles adhering to colorless carrier particles and separated from one another by a minimum distance |
| CN1206313C (en) * | 2000-12-30 | 2005-06-15 | 大连路明发光科技股份有限公司 | New type long-persistence material |
| JP3906075B2 (en) * | 2001-06-07 | 2007-04-18 | 日亜化学工業株式会社 | Monochrome phosphor for FED |
| RU2242545C1 (en) * | 2003-11-04 | 2004-12-20 | Загуменный Александр Иосифович | Scintillation substance (options) |
| JP3872472B2 (en) * | 2003-11-12 | 2007-01-24 | 日亜化学工業株式会社 | Green light emitting yttrium silicate phosphor for projection tube and projection tube using the same |
| US20050189518A1 (en) * | 2004-02-27 | 2005-09-01 | Fuji Photo Film Co., Ltd. | Method of producing a fluorescent particle |
| JP2005320468A (en) * | 2004-05-11 | 2005-11-17 | Fuji Photo Film Co Ltd | Nano particle fluorophor and its dispersion |
| CN101760195B (en) * | 2010-01-22 | 2013-05-08 | 海洋王照明科技股份有限公司 | Silicate blue luminescent material and preparation method thereof |
-
2010
- 2010-07-19 EP EP10854874.4A patent/EP2597133B1/en active Active
- 2010-07-19 WO PCT/CN2010/075246 patent/WO2012009844A1/en active Application Filing
- 2010-07-19 JP JP2013516956A patent/JP5655141B2/en active Active
- 2010-07-19 CN CN201080067223XA patent/CN102933687A/en active Pending
- 2010-07-19 US US13/703,337 patent/US20130075659A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| EP2597133B1 (en) | 2016-12-07 |
| EP2597133A1 (en) | 2013-05-29 |
| EP2597133A4 (en) | 2013-11-27 |
| JP2013533910A (en) | 2013-08-29 |
| US20130075659A1 (en) | 2013-03-28 |
| CN102933687A (en) | 2013-02-13 |
| WO2012009844A1 (en) | 2012-01-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101760195B (en) | Silicate blue luminescent material and preparation method thereof | |
| JP5655141B2 (en) | Silicate luminescent material and preparation method thereof | |
| CN101899308A (en) | Metal nano particle-doped rare earth lanthanum aluminate light-emitting material and preparation method thereof | |
| CN1912049A (en) | High brilliancy environmental protection type alkaline earth ion solid solution titanate fluorescent powder and its preparation method | |
| CN102382646A (en) | Sodium yttrium silicate green luminescent material and preparation method thereof | |
| JP5636099B2 (en) | Zinc-manganese silicate light-emitting material containing metal particles and preparation method thereof | |
| JP5965551B2 (en) | Silicate luminescent material and method for producing the same | |
| CN102134482A (en) | Manganese-doped zinc silicate luminescent material doped with metal nanoparticles and preparation method thereof | |
| US9193901B2 (en) | Metal nanoparticle-coating silicate luminescent material and preparation method therefor | |
| US9416308B2 (en) | Core-shell structured silicate luminescent material and preparation method therefor | |
| JP5913730B2 (en) | Silicate luminescent material containing metal nanoparticles and method for preparing the same | |
| JP5700306B2 (en) | Green light emitting material and preparation method thereof | |
| JP6009091B2 (en) | Aluminate luminescent material and method for producing the same | |
| CN103773362A (en) | Calcium metasilicate luminous material and preparation method for same | |
| JP6034503B2 (en) | Silicate luminescent material and method for producing the same | |
| WO2010099665A1 (en) | Oxide luminescent materials activated by trivalent thulium and their preparations | |
| CN104710987A (en) | Tantalate-based up-conversion luminescent material and preparation method thereof | |
| TWI261613B (en) | Phosphor formulations for low voltage and manufacturing methods thereof | |
| CN103788950A (en) | Rare earth lanthanum aluminate luminescent material and preparation method thereof | |
| TW200951203A (en) | Phosphor materials and methods for fabricating the same | |
| CN103788949A (en) | Rare earth lanthanum aluminate luminescence material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20140221 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20140304 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20140528 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20141104 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20141121 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5655141 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |